CN1169723C - Method for producing lithium manganate and lithium cell using said lithium manganate - Google Patents
Method for producing lithium manganate and lithium cell using said lithium manganate Download PDFInfo
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- CN1169723C CN1169723C CNB008176132A CN00817613A CN1169723C CN 1169723 C CN1169723 C CN 1169723C CN B008176132 A CNB008176132 A CN B008176132A CN 00817613 A CN00817613 A CN 00817613A CN 1169723 C CN1169723 C CN 1169723C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A method for producing lithium manganate which comprises preparing a seed of manganese oxide, subjecting the seed to a particulate growth treatment to provide a granule of manganese oxide having a great diameter, and reacting the resultant manganese oxide with a lithium compound, thereby providing a lithium manganate granule having a great diameter. The lithium manganate produced by the method shows a high packing density due to its great granule diameter, and thus can be used for producing a lithium cell having a high energy density.
Description
Technical field
The present invention relates to a kind of method of producing lithium manganate, lithium manganate is a kind of compound as anode material of lithium battery, the invention still further relates to by using the lithium cell of the lithium manganate acquisition of being produced by this method.
Background technology
Lithium secondary battery has dropped into widespread use in recent years because they have high-voltage, charge-discharge characteristic excellence and also in light weight, size is little, particularly people's tight demand has those lithium secondary batteries of the high electromotive force of 4-V level.As for such lithium secondary battery, the composite oxides of known use cobalt or nickel and lithium are as those lithium secondary batteries of positive electrode active materials; But cobalt and nickel costliness, and the problem of existence possibility resource exhaustion in the future.
Lithium manganate is the composite oxides of manganese and lithium, by chemical formula LiMn
2O
4Expression, and have the spinel type crystal structure, can be as the positive electrode active materials of 4-V level lithium secondary battery.In addition, because raw material manganese is cheap and aboundresources, lithium manganate is promising as the material that can replace cobalt acid lithium and lithium nickelate.
Make its moulding then positive electrode active materials and various additive are mixing, perhaps in addition with solvent formation pasty state, be coated on the substrate then.The lithium manganate that is obtained by traditional wet method only has little particle diameter, even and its roasting grown up the macrobead that can not obtain to wish to carry out particle.Therefore, it presents low bulk density and filling in a large number in fixed volume, so can not obtain the product of high-energy-density.It is generally acknowledged that the tap density of powder increases (being that its specific surface area reduces) with its particle diameter; Therefore, be starved of lithium manganate with macrobead diameter.
JP-A-10-194745 discloses a kind of method that increases the lithium manganate particle diameter, and it comprises manganese oxide is mixed with lithium salts, makes mixture through bakes to burn the article, through handling to reduce degree of crystallinity (for example mechanical mill), passes through roasting for the second time more then.But, in this way, because the reactivity of manganic compound and lithium compound is poor, so, even carry out roasting, also be difficult to obtain to form uniformly, and produce lithium manganate with many lattice imperfections at high temperature.In addition, because product is the inhomogeneous roasting body that is obtained by roasting particle, so particle diameter and particle shape are difficult to control.
JP-A-10-172567 discloses a kind of method, and it comprises Manganse Dioxide or manganic compound are mixed in the aqueous solution with lithium compound, uses dry this mixture of spray-dryer then, with desciccate granulation, roasting then.JP-A-10-297924 discloses a kind of method, and it comprises synthetic lithium manganate powder, makes described powder densification and briquetting then, carries out classification and granulation subsequently, and roasting is granulated then.Although these methods have obtained the lithium manganate as basic substance, it has lattice imperfection seldom and has uniform composition, but particle diameter and particle shape are difficult to control and the particle of finally acquisition is that uneven these difficult problems of roasting body still do not solve.
Summary of the invention
In order to overcome the difficulty of above-mentioned prior art, the purpose of this invention is to provide a kind of method of lithium manganate that is suitable for producing the high-energy-density lithium cell with industrialization and economical advantage, described lithium manganate has big particle diameter and presents high-bulk-density, has homogeneous granules diameter and particle shape and its lattice imperfection is few and form evenly.
After broad research, the inventor has been found that, manganic compound and basic cpd are reacted to each other and oxidation in solution, obtain the manganese oxide seed crystal, manganic compound and basic cpd are reacted to each other in the solution that has the manganese oxide seed crystal, make the reaction product oxidation whereby and it is grown up to the macrobead diameter of hope, when the product that is obtained being used for synthesize lithium manganate, can produce the lithium manganate that has the macrobead diameter and have uniform grading distribution and single-size shape, and in solution, react to each other when above-mentioned manganese oxide and lithium compound, perhaps a part of manganese of described manganese oxide by proton replace with the modified oxidized manganese that improves activity and gained in the aqueous solution, mix with lithium compound or with its reaction, and during product heating that obtains by described any reaction and roasting, can obtain to have the lithium manganate of excellent crystallinity and big particle diameter.
Therefore, according to the present invention, a kind of method of producing lithium manganate is provided, it comprises that (1) makes manganic compound and basic cpd reaction to obtain the step of manganous hydroxide, (2) make the manganous hydroxide oxidation to obtain the step of manganese oxide seed crystal, (3) in the presence of the manganese oxide seed crystal, carry out oxidation and make manganic compound and basic cpd reaction to produce the step that the manganese oxide seed particles is grown up, (4) step that the manganese oxide of growing up through particle and lithium compound are reacted, perhaps with the manganese oxide of the described manganese oxide of acid treatment with the replacement of acquisition proton, step and (5) of then the manganese oxide of proton replacement being mixed with lithium compound or itself and lithium compound being reacted add reaction product or the mixture that thermal bake-out obtains previously.The present invention also provides lithium manganate that a kind of use obtains by the described method lithium cell as positive electrode active materials.
Implement best mode of the present invention
In the present invention, as first step, in liquid medium (as water), react the formation manganous hydroxide by compound and the basic cpd that makes manganese.In order to promote that the reaction that forms manganous hydroxide is preferably carried out in next procedure, i.e. controlled oxidation level in second step in inert atmosphere.Use nitrogen as inert atmosphere in industry with all be favourable aspect economical two.The manganic compound that uses in the 3rd step of first step and back can be a water-soluble manganic compound or a kind of water insoluble but can be made into the manganic compound that acid solution uses, but comparatively preferred with water miscible manganic compound.Used water-soluble manganic compound can be the inorganic manganese compound, as manganous sulfate, Manganous chloride tetrahydrate and manganous nitrate, and organo-manganese compound such as manganese acetate, preferably inorganic manganese compound.Used basic cpd can be the compound of alkali metal hydroxide such as sodium hydroxide, potassium hydroxide and lithium hydroxide and ammonium, as ammonia and ammonia soln.
In a first step, manganic compound can with etc. mole or more the basic cpd of volume neutralize fully.Perhaps can use basic cpd partly to neutralize less than equimolar amount.Part neutralization is preferred, because the manganous hydroxide that is formed by the part neutralization of manganic compound has bigger particle diameter.Be 5-60g/l when carry out manganese ion concentration that part neutralization makes part neutralization back keep in liquid medium, preferably during 10-40g/l, can obtain to have the product of big especially particle diameter.
In ensuing second step, the manganous hydroxide oxidation that obtains in a first step, to form the manganese oxide seed crystal.As mentioned above, can come the particle diameter of controlled oxidation manganese seed crystal by suitably being set in remaining manganese ion concentration in the solution after the part neutralization.When in the above-mentioned scope that remaining manganese ion concentration is adjusted to 5-60g/l, the median size of seed crystal is the 0.1-0.4 micron, and particularly when remaining manganese ion concentration was controlled to be 10-40g/l, it is maximum that the particle diameter of seed crystal reaches, and obtains the median size of 0.3-0.4 micron.Although oxidizing reaction can be carried out in gas phase after established manganous hydroxide is collected with washing after filtration, but, even more preferably by in liquid, being blown into oxidizing gas such as air, oxygen and ozone, perhaps add oxygenant such as aqueous hydrogen peroxide solution and peroxosulphuric hydrogen salt, in liquid phase, carry out oxidizing reaction, carry out because can make oxidizing reaction follow first step like this.
In the 3rd step, in the solution that contains second manganese oxide seed crystal that step obtained (for example aqueous solution), initiate manganic compound or remaining manganic compound and the reaction of initiate basic cpd, by in reaction system, being blown into oxidizing gas or carrying out oxidizing reaction, thereby carry out growing up of seed particles to wherein adding oxygenant.Especially, the use of oxidizing gas is preferred, and using air is preferred as oxidizing gas.Because by suitably setting amount and the adding method of reaction conditions as the basic cpd of adding, can control the particulate growth, uniform grading distributes and the manganese oxide of single-size shape so can obtain to have.Although the degree of oxidation of manganese oxide can be set as requested,, it is oxidized to by molecular formula Mn
3O
4Or 2MnOMnO
2The state of expression.
Used manganic compound and basic cpd are as described in first step.
Equally, in the 3rd step, the reaction of manganic compound and basic cpd also can be undertaken by full dose neutralization or part neutral mode.Full dose neutral method industrial be more favourable because finally there is not remaining unreacted manganic compound.In the part neutralization, almost can not form the little manganese oxide of particle diameter, so this method is favourable for the product that acquisition has uniform shapes and size distribution.For example in carrying out part and the time, residual manganese ion concentration preferably is controlled to be 5-60g/l, more preferably 10-40g/l in liquid medium in part neutralization back; The solution of manganic compound and the solution of basic cpd are preferably parallel to add, because can form more homogeneous granules thus.
In the 4th step, the manganese oxide and the lithium compound of growing up through particle react to each other in liquid medium (as water), perhaps the manganic compound of growing up through particle with acid treatment to obtain the manganese oxide that proton replaces, makes it react with lithium compound in liquid medium (as water) then; Thereby formation manganate precursor for lithium.In addition, the lithium manganate compound of proton replacement mixes in solid phase to form a kind of mixture with lithium compound.Preferably with lithium compound reaction before, with manganese oxide in advance with acid treatment and make it be transformed into the manganese oxide that proton replaces, because improved reactive behavior with lithium compound thus.Though the manganese oxide that proton replaces can mix in liquid phase with lithium compound, perhaps after collecting after filtration, in solid phase, mix with lithium compound, but, two kinds of compounds are reacted to each other, in liquid medium (as water) to form manganate precursor for lithium.Term " manganate precursor for lithium " not only is meant the mixture of manganese oxide and lithium compound, and refers to that lithium ion has entered the material in the manganese oxide crystalline structure, and is as mentioned below.
The lithium compound that can be used for the 4th step for example is lithium hydroxide, lithium nitrate, Quilonum Retard, lithium bicarbonate, lithium chloride and Lithium Sulphate.Wherein particularly preferably be basic cpd such as lithium hydroxide, because they have excellent reactive behavior.The reacting weight of the above-claimed cpd that the ratio of components of manganese and lithium can be by correspondingly in predetermined lithium manganate is controlled.For example, when manganic compound that replaces when proton and lithium compound reacted in aqueous medium, the alkali concn of the reaction liquid that the reacting weight of two kinds of compounds can be by measuring a small amount of sampling was measured.
The manganese oxide of proton replacement in the present invention is by with the formed material of acid treatment manganese oxide, wherein has a part of mn ion in the manganese oxide and is replaced by hydrogen ion.Estimate that the hydrogen ion that replaces is active and easy and other cationic exchange.When the manganese oxide that replaces when proton reacted with lithium compound, lithium ion was easily by entering in the manganese oxide with hydrionic permutoid reaction.Although acid used in acid treatment does not limit especially, it can be mineral acid example hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid, with organic acid such as acetic acid and formic acid, but, mineral acid is preferred, because they are very effective, sulfuric acid or hydrochloric acid are preferred, carry out acid treatment because can have industrial advantage ground.Add the concentration 0.05-10N preferably of acid.The acid concentration that is lower than above-mentioned scope industrial be disadvantageous because the essential acid amount that adds is often too big, and slurry concentration is often too low.The acid concentration that is higher than this scope neither be preferred, because manganese oxide often decomposes then easily.
When the manganese oxide that replaces when manganese oxide and lithium compound or proton reacts to each other in liquid medium (as water) with lithium compound, react and to carry out at 70-250 ℃ usually.In this case, for example when temperature was not higher than 100 ℃, reaction can under atmospheric pressure be carried out, and did not therefore need to use pressure-resistant reaction vessel, and this provides the advantage of practicality; On the other hand, the advantage that is not less than 100 ℃ temperature is to react easier to carry out.Preferred temperature range is 80-230 ℃, and preferred scope is 85-180 ℃.In the reaction under 100 ℃ or the higher temperature, applying pressure container such as autoclave and can depress or carry out hydrothermal treatment consists adding to depress at saturation steam.When air as oxidizing gas, oxygen, ozone etc. or aqueous hydrogen peroxide solution, peroxosulphuric hydrogen salt etc. were provided to reaction system as oxygenant, reaction was easily carried out.Especially, it is preferred using oxidizing gas, and the use air is preferred as oxidizing gas.
The manganese oxide that proton replaces can only react with lithium compound, and is used for ensuing the 5th step with this state.
In the 5th step, manganate precursor for lithium or the manganese oxide of proton replacement and the mixture heating up roasting of lithium compound, to produce lithium manganate.In the present invention, because in the 3rd step, manganese oxide particle has been grown up to the particle diameter near predetermined macrobead lithium manganate, maturing temperature only needs to be not less than the transformation temperature that these materials formation lithium manganates take place.Although maturing temperature can change according to composition and particle diameter, calcination atmosphere and the other factors of above-mentioned presoma or mixture, but it is not less than 250 ℃ usually, preferably be not higher than 850 ℃ in case roasting, more preferably be not less than 280 ℃ and be not higher than 800 ℃.Calcination atmosphere is restriction especially not, as long as it is an oxygen-containing atmosphere, as air; Oxygen partial pressure can be set as requested.
As required can be by the lithium manganate that adds the thermal bake-out acquisition through grinding or fragmentation, perhaps through overcompaction.The method of compacting does not limit especially.Can carry out compacting by the stirring-granulating that uses the compacting that wheel roller, screen cloth shaper (screenforming machine), single-lead-screw extruding briquetting machine, pressure roll, mixer-mill etc. carry out or use mixing machine etc. to carry out.
The lithium manganate that is obtained by the inventive method is a kind of by molecular formula Li
XMn
YO
4The compound of expression, wherein, the value of X/Y is 0.3-1.5 preferably.Particularly preferably be and have spinel type crystalline texture and by molecular formula LiMn
2O
4, Li
4/3Mn
5/3O
4Compound Deng expression.Lithium manganate can comprise the mixture of monophasic lithium manganate or lithium manganate and manganese oxide.
Lithium manganate of the present invention has uniform size distribution and homogeneous granules shape, and has 0.4-50 micron, preferably 0.8-30 micron, the big median size of 1-20 micron more preferably, so that make it can present high tamped density; For example it presents by striking the loose density of the fixed 1.5-2.2g/cc of actual measurement.Therefore therefore, it can be used as positive electrode active materials and is filled in a large number in model or the thickener, during as positive pole, can obtain to have the lithium cell of high-energy-density at the electrode that uses gained.When particle diameter during less than above-mentioned scope, the tap density that can not obtain to be scheduled to; When its during greater than described scope, the lithium cell that uses lithium manganate to make can not have the characteristic of anticipation.The alleged median size of this paper is passed through laser scattering method, and specific surface is measured by the BET method.
Then, the invention provides a kind of lithium cell that uses above-mentioned lithium manganate as positive electrode active materials.Alleged in the present invention lithium cell be to use the lithium metal as the primary cell of negative pole, use metal as the chargeable secondary cell of negative pole with use the chargeable lithium-ion secondary cell as negative pole such as carbonaceous material, tin compound, lithium titanate.Because lithium manganate of the present invention does not almost have lattice imperfection and crystallinity excellence, therefore when it is particularly useful as the positive electrode active materials of lithium secondary battery, the positive pole of crystal disintegration can be obtained when discharging and recharging, to produce hardly, and excellent battery performance can be obtained.In addition, when use has the lithium manganate of the present invention of the crystalline structure that mainly comprises spinel structure, can obtain 3-V level lithium secondary battery, it can discharge and recharge in the scope of about 2-3.5V, and can obtain 4-V level lithium secondary battery, it can discharge and recharge in about 3.5-4.5V scope; Such lithium manganate is useful especially for 4-V level battery.
By in lithium manganate powder of the present invention, adding carbon containing electro-conductive material such as acetylene black, carbon and powdered graphite; With binding agent such as teflon resin and poly(vinylidene fluoride) and mixing and with the mixture forming of gained, can obtain to be used for the positive pole of lithium cell, can use it for coin type battery this moment.In order to be used for cylindrical or rectangular cell, except above-mentioned additive, also by in lithium manganate powder of the present invention, adding organic solvent such as N-Methyl pyrrolidone, with the mixing pasty state form that becomes of the mixture of gained, this mashed prod is coated on the metal current collector (as aluminium foil), dry then, promptly can obtain positive pole.
Being used for electrolyte for Lithium Battery can be the lithium ion solution that is dissolved in the polar organic solvent of electrochemical stability, and the not oxidation in the voltage range wideer than lithium ion battery operating voltage range of promptly described organic solvent is not reduced yet.For example, used polar organic solvent can be Texacar PC, ethylene carbonate, diethyl carbonate, glycol dimethyl ether, tetrahydrofuran (THF), gamma-butyrolactone, and their liquid mixture.For example, the solute as lithium ion source can be lithium perchlorate, lithium hexafluoro phosphate and LiBF4.Porous polypropylene film or polyethylene film are placed between the electrode as barrier film.
For example, described battery comprises coin type battery and cylindrical battery, coin type battery by between the positive pole and negative pole that barrier film are placed on the sheet moulding, pressurization in conjunction with on the sealable shell of being combined to of gained, shell has packing ring that polypropylene makes, pour into ionogen in the shell and seal this shell and obtain; Cylindrical battery is by being coated in positive electrode material and negative material on the metal current collector, reeling, be placed on the molectron of gained in the shell that has packing ring, pour into dielectric medium in the shell and seal this shell and obtain wherein having membranous current collector.In addition, also known a kind of three electrode type batteries, it is used to measure the electrochemical properties of battery.This battery also provides a reference electrode except anodal and negative pole, and estimates the electrochemical properties of each electrode by the voltage of controlling another electrode pair reference electrode.
In order to estimate the performance of lithium manganate, can use metallic lithium etc. to make secondary cell, by in the appropriate voltage scope, discharging and recharging to measure its capacity by continuous current as negative pole as positive electrode material.In addition, by repeated charge, can judge its cycle characteristics performance from volume change.
Embodiment
Describe the present invention in detail below with reference to embodiment, but in any case the present invention is not limited to these embodiment.
Embodiment 1
1. manganous hydroxide is synthetic
In the reactor that stainless steel is made, put into the sodium hydroxide solution and 1.805 premium on currency of 2.57 liter of 8.5 mol.With 5 liters/minute speed when wherein being blown into nitrogen, (press MnSO to wherein adding the 3.744kg manganous sulfate rapidly
4Meter content is 88.06%) be dissolved in the solution that forms in the 15kg water, to neutralize, under agitation condition, 70 ℃ of ageings 3 hours, obtain manganous hydroxide.Residual manganese ion concentration is 30 grams per liters in the solution after the neutralization.
2. the manganese oxide seed crystal is synthetic
In the solution of the manganous hydroxide that obtains, under agitation condition, be blown into the gaseous mixture of air-nitrogen (1: 1) with 5 liters/minute speed above containing, carry out oxidation at 70 ℃, when pH reached 6.4, oxidation finished.Therefore, prepared the manganese oxide seed crystal.
3. the growth of manganese oxide seed crystal
The solution of the manganese oxide that obtains above containing remains on 70 ℃ and when stirring, and is blown into the gaseous mixture of air-nitrogen (1: 1) with 5 liters/minute speed, (presses MnSO to wherein adding the 3.744kg manganous sulfate in 16 hours
4Meter content is 88.06%) be dissolved in the aqueous solution that forms in the 16.843kg water and the sodium hydroxide solution of 2.57 liter of 8.5 mol, neutralizing and oxidation, thereby make the manganese oxide seed crystal grow up.When pH reaches 6.4, extract 20 liters of slurries out, subsequently when in slurry, being blown into the gaseous mixture of air-nitrogen (1: 1), according to step same as described above to wherein adding manganese sulfate solution and sodium hydroxide solution simultaneously, further to carry out growing up of manganese oxide seed crystal.When pH reached 6.4, the reaction of growing up finished, by the solid in the reaction mixture that filters and wash with water collection, to obtain manganese oxide.Residual manganese ion concentration is that (sample a) for 30 grams per liters in the solution when reaction is finished.
4. the manganese oxide of proton replacement is synthetic
Be placed in the stainless steel reactor and be heated to 60 ℃ being dispersed in manganese oxide slurry in the water (counting 700 grams) by manganese.The sulfuric acid that under agitation condition, in 1 hour, in slurry, adds 2.039 liter of 1 mol; Make the mixture reaction 2 hours of gained then, filter then and wash with water, to obtain the manganese oxide that proton replaces.
5. manganate precursor for lithium is synthetic
In the manganese oxide slurry that proton in being dispersed in water replaces (counting 500 grams) by Mn, add a hydronium(ion) oxidation lithium of 5.448 moles and dissolving therein, in this slurry, add entry then so that its volume becomes 1.667 liters, the gained slurry is placed in the glass reactor.In this slurry, be blown into air with 2 liters/minute speed, under agitation condition, slurry be heated to 90 ℃, make its reaction 5 hours.Then, transfer to reaction mixture in the autoclave and 130 ℃ of hydrothermal treatment consists of carrying out 3 hours.Slurry after the hydrothermal treatment consists is placed in the glass reactor once more, simultaneously with 2 liters/minute speed to wherein being blown into air, stirring, and continue 90 ℃ of reactions 1 hour.After reaction, slurry is cooled to 60 ℃, filter then and, obtain manganate precursor for lithium with the washing of the lithium hydroxide solution of 2 liter of 0.1 mol.
6. the roasting of manganate precursor for lithium
Manganate precursor for lithium 110 ℃ of dryings 12 hours, then in air 750 ℃ of roastings 3 hours, obtain lithium manganate.
7. the compacting of lithium manganate
The lithium manganate of roasting above 200 grams is gone up grinding and compacting (sample A) through 30 minutes at small-sized wheel roller (by YOSHIDA SEISAKUSYO CO., LTD. makes).
Embodiment 2
1. manganous hydroxide is synthetic
Obtain manganous hydroxide according to the method identical with embodiment 1.
2. the manganese oxide seed crystal is synthetic
Obtain the manganese oxide seed crystal according to the method identical with embodiment 1.
3. the manganese oxide seed crystal grows up
The solution that contains the manganese oxide seed crystal that obtains above is heated to 70 ℃ and under agitation condition, with 5 liters/minute speed to the gaseous mixture that wherein is blown into air-nitrogen (1: 1).Simultaneously, in 16 hours, (press MnSO to wherein adding the 3.744kg manganous sulfate simultaneously
4Meter content is 88.06%) be dissolved in the aqueous solution in the 16.843kg water and the sodium hydroxide solution of 2.570 liter of 8.5 mol, make the pH value remain on 6.5-7.5 simultaneously, neutralizing and oxidation, thereby make the manganese oxide seed crystal grow up.When pH reaches 6.4, extract 20 liters slurry out, subsequently when in slurry, being blown into the gaseous mixture of air-nitrogen (1: 1), according to step same as described above to wherein adding manganese sulfate solution and sodium hydroxide solution simultaneously, further to carry out growing up of manganese oxide seed crystal.When pH reaches 6.4, extract 20 liters slurry again out, when in slurry, being blown into the gaseous mixture of air-nitrogen (1: 1), in 8 hours, (press MnSO to the aqueous solution that wherein adds the 1.872kg manganous sulfate simultaneously subsequently by 5 liters/minute flow velocity
4Meter content is 88.06%) be dissolved in the aqueous solution that forms in the 8.422kg water and the sodium hydroxide solution of 1.285 liter of 8.5 mol, and maintenance pH value is 6.5-7.5, to carry out further growing up of manganese oxide seed crystal.When pH reached 6.4, the reaction of growing up finished, by filtering and wash with water the solid of collecting in the slurry, to obtain manganese oxide.Residual manganese ion concentration is 30 grams per liters (sample b) in the solution when reaction is finished.
4. the manganese oxide of proton replacement is synthetic
Be placed in the stainless steel reactor and be heated to 60 ℃ being dispersed in manganese oxide slurry in the water (counting 700 grams) by manganese.The sulfuric acid that under agitation condition, in 1 hour, in slurry, adds 2.039 liter of 1 mol; Make the mixture reaction 2 hours of gained then, filter then and wash with water, to obtain the manganese oxide that proton replaces.
5. manganate precursor for lithium is synthetic
In the manganese oxide slurry that proton in being dispersed in water replaces (counting 500 grams) by Mn, add 5.429 mole of one hydronium(ion) oxidation lithium and dissolving therein, in this slurry, add entry then and make that volume is 1.25 liters, and the gained slurry is placed in the glass reactor.In this slurry, be blown into air with 2 liters/minute speed, under agitation condition, slurry be heated to 90 ℃, make its reaction 5 hours.Then, transfer to reaction mixture in the autoclave and 130 ℃ of hydrothermal treatment consists of carrying out 3 hours.Slurry after the hydrothermal treatment consists is placed in the glass reactor once more, simultaneously with 2 liters/minute speed to wherein being blown into air, stirring, and continue 90 ℃ of reactions 1 hour.After reaction, slurry is cooled to 60 ℃, filter then and, obtain manganate precursor for lithium with the washing of the lithium hydroxide solution of 2 liter of 0.1 mol.
6. the roasting of manganate precursor for lithium
Obtain lithium manganate according to the method identical with embodiment 1.
7. the compacting of lithium manganate
According to embodiment 1 in identical method with the lithium manganate compacting.(sample B)
Embodiment 3
1. manganous hydroxide is synthetic
In stainless steel reactor, put into the 3.744kg manganous sulfate and (press MnSO
4Meter content is 88.06%) be dissolved in the solution that forms in the 16.84kg water.With 5 liters/minute speed when wherein being blown into nitrogen, this solution is heated to 70 ℃, and under agitation condition in 1 hour to the sodium hydroxide solution that wherein adds 2.57 liter of 8.5 mol, to neutralize.Then reaction mixture ageing 2 hours, to obtain to contain the solution of manganous hydroxide.Residual manganese ion concentration is 30 grams per liters in the solution after the neutralization.
2. the manganese oxide seed crystal is synthetic
According to embodiment 1 in identical method obtain the manganese oxide seed crystal.
3. the growth of manganese oxide seed crystal
The solution that contains the manganese oxide seed crystal that obtains above is heated to 70 ℃, then under agitation condition, is blown into the gaseous mixture of air-nitrogen (1: 1), in 16 hours, (press MnSO to wherein adding the 3.744kg manganous sulfate simultaneously with 5 liters/minute speed
4Meter content is 88.06%) be dissolved in the aqueous solution that forms in the 16.843kg water and the sodium hydroxide solution of 2.57 liter of 8.5 mol, neutralizing and oxidation, thereby make the manganese oxide seed crystal grow up.When pH reaches 6.4, extract 20 liters slurry out.When in this slurry, being blown into the gaseous mixture of air-nitrogen (1: 1) with 5 liters/minute flow velocity, according to above-mentioned same step to wherein adding manganese sulfate solution and sodium hydroxide solution simultaneously, further to carry out growing up of manganese oxide seed crystal.When pH reaches 6.4, extract the slurry that 20 ascending parts divide again out, subsequently when in slurry, being blown into the gaseous mixture of air-nitrogen (1: 1) by 5 liters/minute flow velocity, according to step same as described above once more to wherein adding manganese sulfate solution and sodium hydroxide solution, further to carry out growing up of manganese oxide seed crystal.When pH reached 6.4, the reaction of growing up finished, by filtering and washing with water, to obtain manganese oxide.Residual manganese ion concentration is 30 grams per liters (sample c) in the solution when reaction is finished.
4. the manganese oxide of proton replacement is synthetic
According to embodiment 2 in identical method obtain the manganese oxide that proton replaces.
5. manganate precursor for lithium is synthetic
In the manganese oxide slurry that proton in being dispersed in water replaces (counting 500 grams) by Mn, add a hydronium(ion) oxidation lithium of 5.373 moles and dissolving therein, in this slurry, add entry then so that its volume becomes 1.111 liters, the gained slurry is placed in the glass reactor.In this slurry, be blown into air with 2 liters/minute speed, under agitation condition, slurry be heated to 90 ℃, make its reaction 5 hours, then, transfer to reaction mixture in the autoclave and 130 ℃ of hydrothermal treatment consists of carrying out 3 hours.Slurry after the hydrothermal treatment consists is placed in the glass reactor once more,, continues under agitation condition 90 ℃ of reactions 1 hour to wherein being blown into air with 2 liters/minute speed.After reaction, slurry is cooled to 60 ℃, filter then and, obtain manganate precursor for lithium with the washing of the lithium hydroxide solution of 2 liter of 0.1 mol.
6. the roasting of manganate precursor for lithium
Obtain lithium manganate according to the method identical with embodiment 1.
7. the compacting of lithium manganate
According to embodiment 1 in identical method with the lithium manganate compacting.(sample C)
Embodiment 4
1. manganous hydroxide is synthetic
Obtain manganous hydroxide according to the method identical with embodiment 3.
2. the manganese oxide seed crystal is synthetic
Obtain the manganese oxide seed crystal according to the method identical with embodiment 1.
3. the manganese oxide seed crystal grows up
In the solution of the manganese oxide seed crystal that above containing, obtains, add 40.260kg water, simultaneously with 5 liters/minute speed to wherein being blown into nitrogen, add the 11.231kg manganous sulfate again and (press MnSO
4Meter content is 88.06%), the mixture of gained is stirred with the dissolving manganous sulfate.The solution of gained is heated to 70 ℃, then under stirring condition, nitrogen is become the gaseous mixture of air-nitrogen (1: 1), and with 5 liters/minute speed to wherein being blown into this gaseous mixture.Subsequently, in 64 hours, add the sodium hydroxide solution of 17.99 liter of 8.5 mol, neutralizing and oxidation, thereby make the manganese oxide seed crystal grow up.When pH reached 8.5, the reaction of growing up finished, and reaction mixture is by filtering and washing with water, to obtain manganese oxide.Residual manganese ion concentration is 0 grams per liter (sample d) in the solution when reaction is finished.
4. the manganese oxide of proton replacement is synthetic
Obtain the manganese oxide that proton replaces according to the method identical with embodiment 1.
5. manganate precursor for lithium is synthetic
In the manganese oxide slurry that proton in being dispersed in water replaces (counting 500 grams) by Mn, add 5.373 mole of one hydronium(ion) oxidation lithium and dissolving therein, in this slurry, add entry then so that its volume becomes 1.111 liters, the gained slurry is placed in the glass reactor.In this slurry, be blown into air with 2 liters/minute speed, under agitation condition, slurry be heated to 90 ℃, make its reaction 15 hours.After reaction, slurry is cooled to 60 ℃, filter then and, obtain manganate precursor for lithium with the washing of the lithium hydroxide solution of 2 liter of 0.1 mol.
6. the roasting of manganate precursor for lithium
Obtain lithium manganate according to the method identical with embodiment 1.
7. the fragmentation of lithium manganate
In agate mortar with the 100 lithium manganate fragmentations of gram after the roastings.(sample D)
Comparative Examples 1
1. manganous hydroxide is synthetic
The 2.397kg manganous sulfate (is pressed MnSO
4Meter content is 88.06%) be dissolved in the solution that forms in the 17.8kg water and be placed in the stainless steel reactor.In this solution, be blown into nitrogen with 5 liters/minute speed, this solution be heated to 70 ℃, under agitation condition in 1 hour to the sodium hydroxide solution that wherein adds 6.825 liter of 4 mol, neutralizing, and obtain manganous hydroxide thus.Residual manganese ion concentration is 0g/l in the solution after the neutralization.
2. manganese oxide is synthetic
When being stirred in the solution that contains manganous hydroxide of Huo Deing, in this solution, be blown into air in the above,, when the pH value reaches 7.0, air become nitrogen, to finish oxidation so that carry out oxidation at 70 ℃ with 5 liters/minute speed.Then reaction mixture is filtered and washes with water, obtain manganese oxide.(sample e)
3. the acid treatment of the manganese oxide of proton replacement
Obtain the manganese oxide that proton replaces according to the method identical with embodiment 1.
4. manganate precursor for lithium is synthetic
In the manganese oxide slurry that proton in being dispersed in water replaces (counting 500 grams) by Mn, add a hydronium(ion) oxidation lithium of 5.675 moles and dissolving therein, in this slurry, add entry then so that its volume becomes 3.846 liters, this slurry is placed in the glass reactor.In this slurry, be blown into air with 3 liters/minute speed, under agitation condition, slurry be heated to 90 ℃, make its reaction 10 hours.After reaction, slurry is cooled to 60 ℃, filter then and, obtain manganate precursor for lithium with the washing of the lithium hydroxide solution of 2 liter of 0.1 mol.
5. the roasting of manganate precursor for lithium
Obtain lithium manganate according to the method identical, but the roasting of manganate precursor for lithium was carried out 3 hours at 800 ℃ with embodiment 1.
6. the compacting of lithium manganate
Carry out compacting (sample E) according to the method identical with embodiment 1.
Comparative Examples 2
Obtain lithium manganate according to the method identical, but the roasting of manganate precursor for lithium is carried out 3 hours (sample F) at 850 ℃ with Comparative Examples 1.
Comparative Examples 3
Obtain lithium manganate according to the method identical, but the roasting of manganate precursor for lithium is carried out 3 hours (sample G) at 900 ℃ with Comparative Examples 1.
Estimate 1
Use specific area measuring equipment (the commodity Monosorb by name that makes by Yuasa Ionics Inc.) and be determined at the manganese oxide seed crystal that obtains among embodiment 1-4 and the Comparative Examples 1-3 or the specific surface area of manganese oxide (sample a-e) and lithium manganate (sample A-G) according to the BET method.
Estimate 2
The aqueous slurry of the manganese oxide seed crystal that obtains in embodiment 1-4 and Comparative Examples 1-3 or manganese oxide (sample a-e) and lithium manganate (sample A-G) is fully disperseed with ultrasonic wave, to obtain laser transmittance is 85 ± 1%, use laser diffraction-scattering system (commodity of being made by Horiba Ltd. are called LA-90) to measure its median size then, by volume.
Estimate 3
The lithium manganate (sample A-G) of every kind 50 gram that obtains in embodiment 1-4 and Comparative Examples 1-3 is placed on 100-ml measures in the cylinder, rap 100 times to measure tapped density.
Estimate 4
Estimate and wherein to be used in the lithium manganate (sample A-G) that obtains among embodiment 1-4 and the Comparative Examples 1-3 charge-discharge characteristic and cycle characteristics as the lithium secondary battery of positive electrode active materials.Described battery is three-electrode system and process repeated charge.The shape and the condition determination of battery are described hereinafter.
Each of above-mentioned sample with as the powdered graphite of electro-conductive material with as the teflon resin of binding agent mixed with 3: 2: 1, mixing in mortar then, become the disk of 14 millimeters of diameters, with the acquisition slice component.The weight of slice component is 50 milligrams.This slice component is placed between the ti-alloy mesh and with the exert pressure of 14.7MPa, with as anodal.
On the other hand, be thickness the disk that 0.5 millimeter metal lithium sheet is shaped to 14 millimeters of diameters, be placed on it between metal nickel screen and the combination of pressurizeing, with as negative pole.Be thickness that 0.1 millimeter metallic lithium foil is on the metal nickel wire, to reach the size that is approximately the rice grain, as reference electrode in addition.As nonaqueous electrolyte, use wherein 1, the solvent mixture of 2-glycol dimethyl ether and Texacar PC (1: 1 by volume), wherein concentration of ordinary dissolution is the lithium perchlorate of 1 mol.Putting in order of electrode is positive pole, reference electrode and negative pole, and porous polypropylene film is placed on therebetween as barrier film.
With the voltage that is set at 4.3-3.5V, under constant current, measure charge/discharge capacity, charging and discharging currents is set at 0.26mA (being about 1 circulation every day).As for cycle characteristics, be determined at for the second time and the 11st round-robin charge/discharge capacity, cycle characteristics is represented [{ 1-(at the charge/discharge capacity of the circulation time second time-at the charge/discharge capacity of the 11st circulation time)/at the charge/discharge capacity of the circulation time second time } * 100] with charge/discharge capacity conservation rate (%).
Specific surface area and the median size of table 1 expression sample a-e, specific surface area, median size and the tapped density of table 2 expression sample A-G, initial charge/discharge characteristic and the cycle characteristics of table 3 expression sample A-G.
Table 1
| Sample | Specific surface area (m 2/g) | Median size (micron) | |
| Embodiment 1 | ?a | ?1.57 | ?4.44 |
| Embodiment 2 | ?b | ?1.59 | ?4.81 |
| Embodiment 3 | ?c | ?1.05 | ?5.78 |
| Embodiment 4 | ?d | ?1.13 | ?5.66 |
| Comparative Examples 1 | ?e | ?21.50 | ?0.51 |
Table 2
| Sample | Specific surface area (m 2/g) | Median size (micron) | Tapped density (g/cm 3) | |
| Embodiment 1 | ?A | ?2.84 | ?3.00 | ?1.85 |
| Embodiment 2 | ?B | ?2.75 | ?3.46 | ?1.98 |
| Embodiment 3 | ?C | ?2.37 | ?4.72 | ?2.00 |
| Embodiment 4 | ?D | ?1.05 | ?6.02 | ?2.02 |
| Comparative Examples 1 | ?E | ?3.70 | ?1.80 | ?1.61 |
| Comparative Examples 2 | ?F | ?3.00 | ?4.01 | ?1.82 |
| Comparative Examples 3 | ?G | ?0.60 | ?7.31 | ?2.00 |
Table 3
| Sample | The initial charge/discharge characteristic | Cycle characteristics capability retention (%) | ||||
| Charging capacity (mAh/g) | Loading capacity (mAh/g) | Efficient (%) | Charging | Discharge | ||
| Embodiment 1 | ?A | ?114.4 | ?112.8 | ?98.6 | ?96.0 | ?95.9 |
| Embodiment 2 | ?B | ?116.2 | ?114.9 | ?98.9 | ?97.9 | ?96.8 |
| Embodiment 3 | ?C | ?119.0 | ?117.0 | ?98.4 | ?96.6 | ?97.2 |
| Embodiment 4 | ?D | ?116.1 | ?114.6 | ?98.7 | ?97.2 | ?97.5 |
| Comparative Examples 1 | ?E | ?117.2 | ?116.9 | ?98.9 | ?93.2 | ?92.8 |
| Comparative Examples 2 | ?F | ?105.4 | ?103.2 | ?97.9 | ?88.2 | ?87.6 |
| Contrast real 3 | ?G | ?100.2 | ?98.8 | ?98.6 | ?85.0 | ?82.1 |
Commercial Application
In the methods of the invention, in the step before producing LiMn2O4, preparation manganese oxide seed crystal also makes it at growth from solution, to form the manganese oxide of large particle diameter. Because the large particle diameter that can obtain to be scheduled to is compared with the method for prior art, can make the particle diameter of final products and grain shape more even, in the method for prior art, form bulky grain by the roasting LiMn2O4 in this step; And, by the condition of suitable setting seeded growth reaction, can control easily particle diameter and grain shape. In addition, manganese oxide and lithium compound through germination react to each other in solution, the manganese oxide that the proton that perhaps obtains by the above-mentioned manganese oxide of acid treatment replaces and lithium compound reaction can obtain the LiMn2O4 that has excellent crystallinity and evenly form. The LiMn2O4 that method of the present invention obtains has aforesaid large particle diameter, presents high-bulk-density and by using it can provide the lithium battery with high-energy-density as anodal active material.
Claims (18)
1. method of producing lithium manganate, this method comprises that (1) makes manganic compound and basic cpd reaction to obtain the step of manganous hydroxide, described manganic compound is to be selected from manganous sulfate, at least a in Manganous chloride tetrahydrate and the manganous nitrate, described basic cpd is selected from alkali metal hydroxide and ammonium compound, (2) with the step of manganous hydroxide oxidation with acquisition manganese oxide seed crystal, (3) in the presence of the manganese oxide seed crystal, make manganic compound and basic cpd the reaction in carry out the step that oxidize manganese seed particles is grown up, (4) step that the manganese oxide of growing up through particle and lithium compound are reacted, perhaps with the manganese oxide of the described manganese oxide of acid treatment with the replacement of acquisition proton, the manganese oxide that proton is replaced mixes or makes step that itself and lithium compound react and (5) and adds the reaction product that thermal bake-out obtains previously or the step of mixture with lithium compound then.
2. according to the method for the production lithium manganate of claim 1, wherein the median size of said lithium manganate is the 0.4-50 micron.
3. according to the method for the production lithium manganate of claim 1, wherein in the reaction of the manganic compound of first step and basic cpd, carry out the part neutralization.
4. according to the method for the production lithium manganate of claim 3, wherein carry out the part neutralization so that residual manganese ion concentration is the 5-60 grams per liter in the solution after the part neutralization.
5. according to the method for the production lithium manganate of claim 1, wherein in second step, carry out oxidation with oxidizing gas or oxygenant.
6. according to the method for the production lithium manganate of claim 5, wherein said oxidizing gas is air, oxygen or ozone, and described oxygenant is aqueous hydrogen peroxide solution or peroxosulphuric hydrogen salt.
7. according to the method for the production lithium manganate of claim 1, wherein when making the reaction of manganic compound and basic cpd, carry out the part neutralization.
8. according to the method for the production lithium manganate of claim 7, wherein carry out the part neutralization so that residual manganese ion concentration becomes the 5-60 grams per liter in the solution after the part neutralization.
9. according to the process of claim 1 wherein that the solution of manganic compound and the solution of basic cpd join in the solution that contains the manganese oxide seed crystal simultaneously in the 3rd step.
10. according to the method for the production lithium manganate of claim 1, wherein in the 3rd step, carry out oxidation with oxidizing gas or oxygenant.
11. according to the method for the production lithium manganate of claim 10, wherein said oxidizing gas is air, oxygen or ozone, described oxygenant is aqueous hydrogen peroxide solution or peroxosulphuric hydrogen salt.
12. according to the method for the production lithium manganate of claim 1, wherein in the 4th step, the acid that is used for handling manganese oxide is be selected from hydrochloric acid, sulfuric acid, nitric acid and hydrofluoric acid at least a.
13. according to the method for the production lithium manganate of claim 1, wherein in the 4th step, the manganese oxide that described manganese oxide or proton replace and the reaction of lithium compound are carried out by means of hydrothermal treatment consists.
14., wherein in the 4th step, when oxidizing gas or oxygenant are provided, carry out the manganese oxide that manganese oxide or proton replace and the reaction of lithium compound in reaction system according to the method for the production lithium manganate of claim 1.
15. according to the method for the production lithium manganate of claim 14, wherein said oxidizing gas is air, oxygen or ozone, oxygenant is aqueous hydrogen peroxide solution or peroxosulphuric hydrogen salt.
16. according to the method for the production lithium manganate of claim 1, wherein in the 5th step, the product that obtains by roasting is through overcompaction.
17. according to the method for the production lithium manganate of claim 1, wherein said lithium compound is to be selected from least a in lithium hydroxide, Quilonum Retard, lithium bicarbonate, lithium chloride and the Lithium Sulphate.
18. the lithium manganate that a use is obtained by the method for claim 1 or 2 is as the lithium cell of positive electrode active materials.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36592899 | 1999-12-24 | ||
| JP365928/1999 | 1999-12-24 |
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|---|---|
| US (1) | US6899860B2 (en) |
| EP (1) | EP1243556B1 (en) |
| KR (1) | KR100638132B1 (en) |
| CN (1) | CN1169723C (en) |
| AT (1) | ATE353854T1 (en) |
| AU (1) | AU2222201A (en) |
| DE (1) | DE60033433T2 (en) |
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| WO (1) | WO2001047814A1 (en) |
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| US20070266554A1 (en) * | 2006-05-16 | 2007-11-22 | Bruce Gregg C | Electrochemical cell with moderate-rate discharging capability and method of production |
| US8846225B2 (en) * | 2008-02-22 | 2014-09-30 | Steven E. Sloop | Reintroduction of lithium into recycled battery materials |
| US20110311437A1 (en) * | 2010-06-21 | 2011-12-22 | Ngk Insulators, Ltd. | Method for producing spinel-type lithium manganate |
| US20110311435A1 (en) * | 2010-06-21 | 2011-12-22 | Ngk Insulators, Ltd. | Method for producing spinel-type lithium manganate |
| CN102432070B (en) * | 2011-09-21 | 2013-09-18 | 江西博能新材料有限公司 | Preparation method for precursor for lithium manganate and lithium manganate anode material |
| KR101480109B1 (en) * | 2013-02-06 | 2015-01-07 | 한국세라믹기술원 | Synthesis Method of Nano-Chemical Manganese Dioxide by Recycle Process for Cathode material used in Secondary Battery |
| EP3054508A4 (en) * | 2013-10-03 | 2017-08-16 | GS Yuasa International Ltd. | Positive electrode active material for lithium secondary battery, method for manufacturing same, lithium secondary battery electrode, lithium secondary battery, and electric storage device |
| CN111601656A (en) * | 2018-04-20 | 2020-08-28 | 住友金属矿山株式会社 | Method for producing precursor of lithium adsorbent |
| WO2020097554A1 (en) | 2018-11-09 | 2020-05-14 | Basf Corporation | A process for producing lithiated transition metal oxides |
| CN110224137B (en) * | 2019-05-28 | 2022-06-24 | 中南大学 | Method for directionally constructing interface modification layer of manganese-containing material |
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| US5639438A (en) * | 1995-12-06 | 1997-06-17 | Kerr-Mcgee Chemical Corporation | Lithium manganese oxide compound and method of preparation |
| JPH10172567A (en) | 1996-12-17 | 1998-06-26 | Nikki Kagaku Kk | Manufacture of lithium manganate |
| JPH10194745A (en) | 1996-12-27 | 1998-07-28 | Tosoh Corp | Production of lithium manganese compound oxide and its use |
| JP4086931B2 (en) | 1997-04-23 | 2008-05-14 | 日本電工株式会社 | Method for producing high density spinel type LiMn2O4 |
| JPH10310428A (en) | 1997-05-08 | 1998-11-24 | Ishihara Sangyo Kaisha Ltd | Lithium titanate hydrate and production of lithium titanate |
| JPH1116574A (en) * | 1997-06-23 | 1999-01-22 | Toyota Central Res & Dev Lab Inc | Lithium manganese composite oxide and its manufacture |
| JPH11180717A (en) * | 1997-12-22 | 1999-07-06 | Ishihara Sangyo Kaisha Ltd | Lithium manganate, its production and lithium cell produced by using the same |
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| US20030027047A1 (en) | 2003-02-06 |
| DE60033433T2 (en) | 2007-11-15 |
| CN1413171A (en) | 2003-04-23 |
| EP1243556A1 (en) | 2002-09-25 |
| KR20020086868A (en) | 2002-11-20 |
| ATE353854T1 (en) | 2007-03-15 |
| DE60033433D1 (en) | 2007-03-29 |
| US6899860B2 (en) | 2005-05-31 |
| EP1243556B1 (en) | 2007-02-14 |
| KR100638132B1 (en) | 2006-10-24 |
| TWI239934B (en) | 2005-09-21 |
| AU2222201A (en) | 2001-07-09 |
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| EP1243556A4 (en) | 2005-08-17 |
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